[Paper Review] Effect of substrate mismatch, orientation, and flexibility on heterogeneous ice nucleation

Miguel Camarillo, J. Oller-Iscar+3 more|arXiv (Cornell University)|Jan 10, 2026

nanoparticles nucleation surface interactions0 citations

TL;DR

The study quantifies how lattice mismatch, substrate orientation, and lattice flexibility impact heterogeneous ice nucleation using water-based substrates and the mW model. It finds about 4 K fewer nucleation temperature per 1% mismatch, similar nucleation ability across ice orientations, and higher nucleation efficiency for flexible substrates.

ABSTRACT

Heterogeneous nucleation is the main path to ice formation on Earth. The ice nucleating ability of a certain substrate is mainly determined by both molecular interactions and the structural mismatch between the ice and the substrate lattices. We focus on the latter factor using molecular simulations of the mW model. Quantifying the effect of structural mismatch alone is challenging due to its coupling with molecular interactions. To disentangle both factors, we use a substrate composed of water molecules in such a way that any variation on the nucleation temperature can be exclusively ascribed to the structural mismatch. We find that a one per cent increase of structural mismatch leads to a decrease of approximately 4 K in the nucleation temperature. We also analyse the effect of the orientation of the substrate with respect to the liquid. The three main ice orientations (basal, primary prism and secondary prism) have a similar ice nucleating ability. We finally asses the effect of lattice flexibility by comparing substrates where molecules are immobile with others where a certain freedom to fluctuate around the lattice positions is allowed. Interestingly, we find that the latter type of substrate is more efficient in nucleating ice because it can adapt its structure to that of ice.

Motivation & Objective

• Isolate and quantify the effect of lattice mismatch on ice nucleation independent of inter-molecular interactions.
• Determine how different ice-substrate orientations affect nucleation ability.
• Assess the role of substrate lattice flexibility on nucleation efficiency.
• Provide mechanistic insight into interfacial structure during nucleation on mismatched substrates.

Proposed method

• Use the mW water model in LAMMPS in the NVT ensemble to simulate ice nucleation on stretched water-substrates.
• Construct substrates by stretching/compressing an ice unit cell at coexistence; define structural mismatch delta = 100*|f-1|.
• Compare two substrate types: rigid (immobile) and wells (atoms can wander within a potential well).
• Quantify nucleation by measuring induction times and computing J = 1/(2 A t_ind), defining T_n at log(J/(m^2 s)) = 23.6.
• Analyze interface structure via radial distribution functions and q12 local bond order parameter across slabs near the interface.
• Examine three ice orientations exposing the substrate: basal, primary prism (pI), and secondary prism (pII).

Figure 3: (a) Potential energy versus time for a trajectory at 272 K (1 K below the melting temperature) on a wells substrate with $\delta=0$ . (b) Potential energy versus time for nine trajectories of a liquid at 245.0 K on a wells substrate with $\delta=7$ . (c) Time evolution of the potential ene

Experimental results

Research questions

• RQ1 How does lattice mismatch between ice and a substrate affect the nucleation temperature under fixed area and observation time?
• RQ2 Do the three main ice orientations (basal, pI, pII) show similar nucleation abilities on stretched water substrates?
• RQ3 What is the impact of substrate lattice flexibility on heterogeneous ice nucleation?
• RQ4 How does isotropic stretching vs compression of the substrate influence nucleation temperature and rate?
• RQ5 What are the structural characteristics of the liquid layer and nucleus near the interface during nucleation on mismatched substrates?

Key findings

• A 1% increase in structural mismatch roughly lowers the nucleation temperature by about 4 K (for both rigid and wells substrates).
• Nucleation rate versus temperature curves are parallel across mismatches, enabling a linear-like trend of T_n with delta that extrapolates toward the coexistence point (delta=0).
• The three ice orientations (basal, pI, pII) exhibit very similar nucleation abilities, with small differences in efficiency.
• Flexible (wells) substrates nucleate ice at higher temperatures (by ~1–2 K) than rigid substrates due to the substrate’s ability to adapt to the ice structure.
• Liquid structure near the interface becomes more ice-like as mismatch decreases, with evidence of heterogeneous, patchy ice-like regions rather than a uniform wetting layer; nuclei show tilted molecular columns indicating gradual structural recovery from substrate to bulk ice.

Figure 4: (a) Heterogeneous nucleation rate versus temperature for the different mismatches and the different kinds of stretched substrates studied in this work as indicated in the legend. These results correspond to the pII orientation (exposing the yz plane of the stretched and replicated unit cel